Coated conductor high temperature superconductor carrying high critical current under magnetic field by intrinsic pinning centers, and methods of manufacture of same

ABSTRACT

A coated conductor comprises a substrate supporting a ReBCO superconductor adapted to carry current in a superconducting state. The superconductor is characterized in having peaks in critical current (J c ) of at least 0.2 MA/cm 2  in a magnetic field of about 1 Tesla when the field is applied normal to the surface of the superconductor and when the field is applied parallel to the surface of the superconductor, and further characterized in that the superconductor includes horizontal defects and columnar detects in a size and an amount sufficient to result in the said critical current response. The conductor is characterized in that the ratio of the height of the peaks in the J c  is in the range from 3:1 with the ratio of the field perpendicular (0 degrees) to the field parallel (+/−90 degrees) to the range from 3:1 with the ratio of the field parallel to the field perpendicular.

PRIORITY CLAIM

This application is a continuation of application Ser. No. 14/047,672, filed Oct. 7, 2013 (our Reference 844,004-415); which is a continuation-in-part of application Ser. No. 13/369,186 filed Feb. 8, 2012, now U.S. Pat. No. 9,362,025 (our Reference 844,004-412), which are hereby incorporated by reference as if fully set forth herein.

FIELD OF THE INVENTION

The present invention relates to coated conductor high temperature superconductor (HTS) conductors having high in-field current and current carrying capacity. More particularly, the coated conductors are formed as superconducting wires.

While no claims of priority are being made to the following cases, they include relevant subject matter: Ruby, et al., “High-Throughput Deposition System for Oxide Thin Film Growth By Reactive Coevaporation”, now published as US Published Application 2007/0125303 and Moeckly et al., “RF-Properties Optimized Compositions of (RE)Ba₂Cu₃O_(7-δ) Thin Film Superconductors”, now issued as U.S. Pat. No. 7,867,950. Both of these are incorporated herein by reference as if fully set forth herein in their entirely.

BACKGROUND THE INVENTION

The last 25 years have shown significant advancements in the performance properties of high temperature superconductors. With those improving performance properties has come the desire to utilize HTS for the practical application of loss-free electrical power transmission and other energy saving applications in the development of the smart grid and other energy related applications.

Early efforts, sometimes termed the first generation (1G) HTS, to form wires did not yield technically or commercially acceptable solutions. The superconductors typically used wire drawing technology, often using variations on Bi₂Si₂Ca₂O₇. Unfortunately, the HTS was too brittle and costly due to high silver content for the intended applications.

Efforts in the so-called second generation (2G) HTS have focused on using a thin layer of high quality HTS usually (RE)BaCuO (also known as (RE)BCO, and where (RE) is a rare earth such as yttrium, samarium, gadolinium, neodymium, dysprosium, etc.) usually on a flexible metal substrate. Such 2G HTS is capable of maintaining a dissipation free state while still carrying large electrical currents even in the presence of a large magnetic field such as is found in motor and generator applications. Most proposed solutions adopt the addition of materials beyond the basic components of the HTS in order to provide extrinsic pinning centers. For example, prior art focuses on adding extra pinning centers by incorporating extra elements during film growth, e.g. Zr, Ta, Nb, Sn. Adding these extrinsic elements to (RE)BCO makes the process more complicated and also raises cost. Despite these clear drawbacks, the field relatively uniformly follows this approach. See, e.g., Foltyn et al., “Materials Science Challenges for High-Temperature Superconducting Wire”, Nature Materials, Vol. 6, September 2007, pp. 631-641, Maiorov, et al., “Synergetic Combination of Different Types of Defect to Optimize Pinning Landscape Using BaZrO₃-doped YBa₂Cu₃O₇”, Nature Materials, Vol. 8, May 2009, pp. 398-404, Zhou, et al., “Thickness Dependence of Critical Current Density in YBa₂Cu₃O₇-δ Films with BaZrO₃ and Y₂O₃ Addition, “Supercond. Sci. Technol. 22 (2009), pp. 1-5, Sung Hun Wee, Amit Goyal, and Yuri L. Zuev, “Growth of thick BaZrO₃-doped YBa₂Cu₃O_(7-δ) films with high critical currents in high applied magnetic fields”, IEEE Transactions on Applied Superconductivity, Volume 19, Number 3, June 2009, pp. 3266-3269, Amit Goyal, M. Parana Paranthaman, and U. Schoop, “The RABiTS Approach: Using Rolling-Assisted Biaxially Textured Substrates for high-performance YBCO superconductors”, MRS Bulletin, August 2004, pp. 552-561, T Aytug, M Paranthaman, E D Specht, Y Zhang, K Kim, Y L Zuev, C Cantoni, A Goyal, D K Christen, V A Maroni, Y Chen, and V Selvamanickam, “Enhanced flux pinning in MOCVD-YBCO films through Zr additions: systematic feasibility studies”, Superconductor Science and Technology Volume 23 (2010), Sung Hun Wee, Amit Goyal, Eliot D, Specht, Claudia Cantoni, Yuri L. Zuev, V, Selvamanickam, and Sy Cook, “Enhanced flux pinning and critical current density via incorporation of self-assembled rare-earth barium tantalate nanocolumns within YBa₂Cu₃O_(7-δ) films”, Rapid Communications, Physical Review B Volume 81 (2010), Amit Goyal, Claudia Cantoni, Eliot Specht, Song-Hun Wee, “Critical current density enhancement via incorporation of nanoscale Ba₂(Y,Re)TaO₆ in REBCO films”, US Patent Application publication US2011/0034338A1, Feb. 10, 2011.

Another approach which has proved less promising to date is introducing microstructural defects, into the HTS. See, for example, Selvamanickam published US Application 2011/0028328 which suggests use of a complex surface treatment including the formation of nanorods grown on an array of nanodots, especially nanorods of BZO. In a document dated after the effective filing date of that application, it was stated that while doping with Zr can result in BZO nanocolumns, it necessitated a “substantially reduced deposition rate”. Selvamanickam et al, “High Critical Current Coated Conductors”, CRADA Final Report For CRADA Number ORNL02-0652 (2011). See also, Foltyn et al, where multiple interlayers of CeO2 are grown within the (RE)BCO film to introduce structural defects, and H. Wang et al. U.S. Pat. No. 7,642,222, issued Jan. 5, 2010, where SrTiO₃ layers with varied microstructure are used as the seed layer for growth of the (RE)BCO film.

Other investigators have reported on process dependent limitations, such as critical current saturation as a function of film thickness, for coated conductors formed via pulsed laser deposition. See, e.g., Inoue, “In-Field Current Transport Properties of 600 A-Class GdBa₂Cu₃O_(7-δ) Coated Conductor Utilizing IBAD Template”, IEEE Transactions on Applied Superconductivity, Vol. 21, No. 3, June 2011. A 2.5 μm thick GdBCO film was made by pulsed laser deposition on a Hastelloy substrate, with a 1.1 μm thick GdZrO₇ layer made by ion-beam assisted deposition (IBAD), and a 0.5 μm thick CeO₂ layer formed by pulsed laser deposition. A silver protection layer was provided. The measured sample was formed from a 1 cm long piece, formed into a microbridge 70 μm width by 500 μm length. Critical current at 77K and self-field were 600 A/cm-w, and critical temperature was 93 K.

Despite the clear desirability of a coated conductor achieving these objects, the need remains for a comprehensive and effective solution having high yield and low cost in commercially useable lengths.

SUMMARY OF THE INVENTION

A coated conductor comprises a substrate supporting a (Re)BCO superconductor adapted to carry current in a superconducting state. The superconductor is characterized in having a minimum critical current density (J_(c)) of at least 0.2 MA/cm² at 77 K in a magnetic field of 1 Tesla when the field is applied at all angles relative to the superconductor. It is further characterized in that the ratio of the height of the peaks in the J_(c) is in the range from 3:1 with the ratio of the field perpendicular (0 degrees) to the field parallel (+/−90 degrees) to the range from 3:1 with the ratio of the field parallel to the field perpendicular. It is further characterized in that the superconductor includes horizontal defects and columnar defects in a size and an amount sufficient to result in the said critical current response.

A coated conductor comprises a substrate supporting a ReBCO superconductor adapted to carry current in a superconducting state. The superconductor is characterized in having peaks in critical current (J_(c)) of at least 0.2 MA/cm² at 77 K, and more preferably 0.5MA/cm² at 77 K in a magnetic field of about 1 Tesla when the field is applied normal to the surface of the superconductor and when the field is applied parallel to the surface of the superconductor, and further characterized in that the superconductor includes horizontal defects and columnar defects in a size and an amount sufficient to result in the said critical current response. The ratio of the peak Jc to the minimum Jc as a function of angle is preferably at most less than 3, more preferably at most less than 2, and most preferably at most less than 1.3. The relative height of the peak in the critical current when the magnetic field is applied normal to the surface of the superconductor relative to the peak when the field is applied parallel to the surface is preferably greater than 50%, more preferably greater than 75%, and most preferably substantially equal to 100%.

In yet another aspect, a coated superconductor comprises a substrate and a (Re)BaCO superconductor supported by the substrate, the superconductor adapted to carry current in a superconducting stale, where Re is a rare earth, Ba is barium, C is copper and O is oxygen, where the ratio of B to Re is in the range from 1.4 to 2.1, preferably around substantially 1.73, and the atomic percent copper is between substantially 50% and 55%. It is further characterized in that the ratio of the height of the peaks in the J_(c) is in the range from 3:1 with the ratio of the field perpendicular (0 degrees) to the field parallel (+/−90 degrees) to the range from 3:1 with the ratio of the field parallel to the field perpendicular. The superconductor may be characterized in the relative height of the peak in the critical current when the magnetic field is applied normal to the surface of the superconductor relative to the peak when the field is applied parallel to the surface is greater than substantially 50%, more preferably greater than 75%, and most preferably substantially equal to 100%.

In yet another aspect, a coated superconductor product formed by the specified process comprises a substrate, and a (Re)BaCO superconductor supported by the substrate, the superconductor adapted to carry current, in a superconducting state, where Re is a rare earth, B is barium, C is copper and O is oxygen, where the ratio of B to Re is in the range from 1.4 to 2.1, and the atomic percent copper is between substantially 50% and 55%. The product is characterized in that the ratio of the height of the peaks in the J_(c) is in the range from 3:1 with the ratio of the field perpendicular (0 degrees) to the field parallel (+/−90 degrees) to the range from 3:1 with the ratio of the field parallel to the field perpendicular. The superconductor may be characterized in the relative height of the peak in the critical current, when the magnetic field is applied normal to the surface of the superconductor relative to the peak when the field is applied parallel to the surface is greater than substantially 50%, more preferably greater than 75% and more preferably substantially 100%. The product is preferably formed by the process including reactive coevaporation cyclic deposition and reaction techniques.

A 2^(nd) generation HTS coated conductor is provided having a substrate and a (RE)BaCO superconductor supported by the substrate, The superconductor is adapted to carry current in a superconducting state, with the superconductor having a current (I) carrying capacity of at least 250 A/cm width, in a field of 3 Tesla (T), at 65 Kelvin (K), at all angles relative to the coated conductor. More preferably, the current carrying capacity extends through the range of substantially 250 A/cm to 500 A/cm. Preferably, the coated conductor has a critical current (I_(c)) carrying capacity of at least 250 A/cm width, in a field of 3 T, at 65 K, at all angles relative to the coated conductor. Preferably, the coated conductor has a critical current density (J_(c)) carrying capacity of at least 0.5, and more preferably, at least 0.55, MA/cm² in a field of 3 T, at 65 K, at all angles relative to the coated conductor.

In yet another aspect of the invention, a multilayer structure is provided, having at least a substrate and (RE)BACO superconductor having the properties stated, above. The substrate may be non-flexible, such as a crystal substrate, preferably an MgO crystal, substrate. Alternately, the substrate may be flexible, such as a flexible metal tape, preferably made of non-magnetic alloy, such as Hastelloy or stainless steel. Optionally, the substrate is subject to a planarization process, preferably a solution deposition planarization process. Preferably, the planarization process provides a Y₂O₃ or other metal oxide solution deposition planarization layer, An optional intermediate layer may be formed between the substrate, or planarization layer if present, and the superconductor layer. Preferably, the intermediate layer is formed by ion beam assisted deposition (IBAD) to form a highly oriented crystalline layer, more preferably an MgO IBAD crystalline layer, followed by an epitaxial MgO layer, more preferably formed by evaporation or sputtering. The (RE)BaCO layer is preferably formed via a reactive co-evaporation-cyclic deposition and reaction (RCE-CDR) process. Optional buffer layers and capping layers may be provided.

In yet another aspect, a multi-layer coated conductor is formed having a substrate and a (RE)BaCO superconductor supported by the substrate, the superconductor adapted to carry current in a superconducting state, where that structure is formed by the process and method steps of, first, providing a first substrate having a first face, second, planarizing at least the first face of the substrate to form a planarized surface, third, forming an ion beam assisted deposition epitaxial layer on the planarized surface, and lastly forming the (RE)BaCO superconductor in a layer supported by the epitaxial layer. Additional optional layers may be formed between or on those layers mentioned. Preferably, the planarizing is performed via solution deposition planarization. Also preferably, the ion beam assisted deposition epitaxial layer is an MgO layer.

In yet another aspect of the invention, a multi-layer coated conductor has a substrate having a first face, the substrate having a length dimension of at least one meter, an epitaxial layer supported by the substrate, and a (RE)BaCO superconductor layer supported by the epitaxial layer, the layer having a thickness of at least 2 microns and a length of at least one meter, the superconductor adapted to carry current in a superconducting state, having an critical current (I_(c)) of at least 100 A/cm width at a temperature of 65 K in a field of 3 Tesla at all angles. More preferably, the conductor has a critical current of at least 200 A/cm width at a temperature of 65 K in a field of 3 Tesla at all angles. Most preferably, the conductor has a critical current of at least 200 A/cm width at a temperature of 65 K in a field of 3 Tesla at ail angles.

In yet another aspect of these inventions, a multi-layer coated conductor has a substrate having a first face, a planarization layer disposed adjacent the first face of the substrate, a ion beam assisted deposition epitaxial layer supported by the planarization layer, and a (RE)BaCO superconductor supported by the epitaxial layer, the superconductor adapted to carry current in a superconducting state, having an critical current (I_(c)) of at least 50 A/cm, more preferably 100 A/cm, and most preferably 200 A/cm, at a temperature of 77 K and no external magnetic field (self field).

One object of this invention is to produce HTS material with intrinsic pinning centers on an industrial scale and at a low cost. This invention preferably avoids additional elements in order to maintain high critical current density under high DC magnetic field. This invention utilizes intrinsic pinning centers that maintain high critical current in high fields at high temperatures. The key steps in the processes are all inherently scalable to large area, long length and high throughput, making them ideal for industrial applications. Also this approach makes it possible to reduce the number of process steps, therefore, lowering the overall cost for the final product by reducing the raw material used and also saving capital equipment expenditure. Additionally the high throughput and modest capital expenditure of these processes means that the cost of capital is low. Finally, since the HTS is grown on layers built on low cost flexible metal, tape, the raw material cost is low.

Yet other objects of the inventions are to provide for an inherently scalable process, having reduced number of process steps per layer, with high throughput. This should result in a large HTS growth area.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional view of a coated conductor.

FIG. 2 is a perspective drawing of the solution deposition planarization (SDP) equipment and method.

FIG. 3 is an exploded cross-sectional view of a substrate and planarization layer after the solution deposition planarization process.

FIG. 4 is a perspective drawing of the ion beam assisted deposition equipment and method.

FIG. 5 is a perspective drawing of the reactive co-evaporation, cyclic deposition and reaction (RCE-CDR) equipment and method.

FIG. 6 is a TEM image of a ReBaCO film and metal capping layer.

FIG. 7 is a higher magnification TEM image of a portion of the ReBaCO film of FIG. 6.

FIG. 8 is a graph of the critical current (J_(c) expressed in MA/cm²) as a function of angular orientation under a magnetic field of 1 Tesla of the sample of FIGS. 6 and 7.

FIG. 9 is a TEM image of a ReBaCO film showing dislocations along the c-axis and particles along the a, b-axis.

FIG. 10 is a higher magnification TEM image of a portion of the ReBaCO film of FIG. 9, showing both the c-axis columnar defects and particles along the a, b-axis.

FIG. 11 is a graph of the critical current (J_(c) expressed in MA/cm²) as a function of angular orientation under a magnetic field of 1 Tesla of the sample of FIGS. 9 and 10.

FIG. 12 is a graph of the critical current Ic as a function of angle from the c-axis in degrees for a sample with Ba/Sm ratio of 1.57.

FIG. 13 is a graph of the critical current Ic as a function of angle from the c-axis in degrees with a Ba/Sm ratio of 1.76.

FIG. 14 is a graph of the critical current Ic as a function of angle from the c-axis in degrees with a Ba/Sm ratio of 2.02.

FIG. 15 is a graph of the critical current density Jc as a function of angle from the c-axis in degrees with varying ratios of relative rare earth %, ranging from −5% to 20%.

FIG. 16 is a graph of the critical current density Jc as a function of angle from the c-axis in degrees in a sample with the vertical dislocations shown in FIG. 17.

FIG. 17 is a microphotograph showing the vertical dislocations resulting in the strong c-axis peak of FIG. 16.

FIG. 18 is a plot of the critical current (I_(c)) (left vertical axis) and critical current density (J_(c)) (right vertical, axis) as a function of magnetic field strength, applied parallel, to the sample, for two different temperatures.

FIG. 19 is a plot of the critical current (I_(c)) (left vertical axis) and critical current density (J_(c)) (right vertical axis) as a function of the angle from the c-axis applied to the sample.

FIG. 20 is a plot of the critical current (I_(c)) (left vertical axis) and critical current density (J_(c)) (right vertical axis) as a function of the angle of the magnetic field from the c-axis.

FIG. 21 is a plot of the critical current (I_(c)) (left vertical axis) and critical, current, density (J_(c)) (right vertical axis) as a function of magnetic field strength applied parallel to the sample, at two different temperatures.

FIG. 22 is a plot of the critical, current density (I_(c)) (left vertical axis) and critical current (I_(c)) (right vertical axis) as a function the angle of the magnetic field from the c-axis.

FIG. 23 is a plot of the critical current density (J_(c)) as a function of the angle of the magnetic field from the c-axis for three differently prepared samples of NdBCO

FIG. 24 is a plot of the critical current density (J_(c)) as a function of the angle of the magnetic field from the c-axis for three differently prepared samples of SmBCO and one sample of NdBCO.

FIG. 25 is a plot of the critical current density (J_(c)) as a function of the angle of the magnetic field from the c-axis

FIGS. 26 A and B show X-ray diffraction scan showing 2θ−ω and ω scans for: FIG. 26A YBCO on MgO single crystal and FIG. 26B YBCO on IBAD/epitaxial MgO on SDP Hastelloy.

FIG. 27 is a X-ray diffraction 2θ−ω to scan showing SmBCO on IBAD MgO and SDP on Hastelloy.

FIG. 28 is a X-ray diffraction pole figure of (RE)BCO (103) peak.

FIG. 29 is an atomic force microscope (AFM) image of (RE)BCO grown on a metal substrate, and then capped with silver.

FIG. 30 is a graph of resistivity as a function of temperature of a sample of SmBCO grown on single crystal MgO.

FIGS. 31 A, B and C are graphs of critical current (I_(c)) under magnetic field of 0.66 T as a function of position along a tape for a 70 cm long tape (FIG. 31A), a 120 cm long tape (FIG. 31B) and a 24 cm long tape (FIG. 31C), for self-field at 77 K.

DETAILED DESCRIPTION OF THE INVENTION Definitions

“ReBaCuO superconductor” means tare earth (Re), barium (Ba), copper (Cu) and oxygen (O) containing compositions that constitute superconductors at cryogenic temperatures.

“Substantially pure ReBaCuO superconductor” means a ReBaCuO superconductor that contains less than 2%, preferably less than 1%, most preferably less than 0.5% by weight of materials other than Re, Ba, Cu and O.

Structure and Process

FIG. 1 shows a cross-section of one embodiment of the coated conductor 10. At least a substrate 12 and (RE)BCO layer 14 are provided. The substrate 12 supports, either directly or through the presence of one or more intermediate layers, the (RE)BCO(RE)BCO layer 14. Optionally, a solution deposition planarization layer 16 is formed at the surface of the substrate 12. The solution deposition planarization layer 16 may then directly support the (RE)BCO layer 14, or may interface with an intermediate layer 18. In one implementation, the intermediate layer 18 may be an IBAD epitaxial layer, such as an IBAD epitaxial MgO layer. The intermediate layer 18 may directly support the (RE)BCO layer 14, or may interface with a optional buffer layer 20, such as CeOl, which in turn can support the (RE)BCO layer 14, Additional layers may be disposed on the (RE)BCO layer 14. such as a capping layer 22, or other metals, such as one or more of copper, brass, silver and stainless steel.

The substrate may be either non-flexible or flexible. If non-flexible, it may be a crystal substrate, such as an MgO substrate. If the substrate is flexible, it may be for example a flexible metal tape. In one implementation, substrate 10 is a flexible metal substrate that can for example be stainless steel or Hastelloy, The thickness of the substrate is often in the range of 0.002 to 0.004 inch. The substrate material must meet certain selection criteria: it must be mechanically and chemically stable at the growth temperature of the superconductor (˜800 C), it must have a thermal expansion coefficient similar to the superconductor (˜12-13), a high yield strength, and be non-magnetic. While the surface smoothness of the substrate will depend upon the particular material and the preparation of the material, a crystalline substrate may be very smooth, whereas a metal substrate may have surface roughness such as in the range of 25 to 50 nm.

With reference to FIGS. 2 and 3, an optional planarization step is performed. The planarization provides an amorphous metal oxide layer that is solution deposited preferably using a solution deposition planarization (SDP) process on the substrate. This one layer provides a diffusion barrier, planarizes the rough metal surface, is chemically stable and provides an amorphous surface suitable for the growth of subsequent layers. Often to otherwise accomplish all of these features several separate steps including electropolishing, the addition of a diffusion barrier and a amorphous bed layer for ion beam assisted deposition (IBAD), would be required. Substrate tape stock 24 may be fed from a spool into a bath 26 containing the planarization solution. The coated conductor passes through dryer 28 onto a take up spool having the now planarization layer coated substrate 30. FIG. 3 shows an exploded view of the substrate 12 and the solution deposition planarization layer 16.

The solution deposition planarization (SDP) process uses metal organic precursor dissolved in solvent. This solution can be applied to the metal substrate utilizing techniques such as dip coating, spray coating, meniscus coating or slot die coating. The solution deposited on the metal substrate travels into a heater where the solvent is evaporated out, and the organic carrier is volatilized leaving behind only the dense, amorphous, metal oxide film. Preferably, the resulting multiple coatings deposited by sequentially repeating this process creates a smooth (roughness ˜1 nm), planarized, chemically stable, and amorphous surface.

With reference to FIG. 4, the optional next layer is deposited using an ion beam assisted deposition (IBAD) technique. A metal oxide having a rock-salt-like crystal structure, usually MgO, is deposited with the assistance of an ion beam (see, e.g., Do et al., U.S. Pat. No. 6,190,752 entitled “Thin Films Having Rock-Salk-Like Structure Deposited on Amorphous Surfaces”, see also Wang, et al., “Deposition of in-plane textured MgO on amorphous Si₃N₄ substrates by ion-beam-assisted deposition and comparisons with ion-beam-assisted deposited yttria-stabilized-zirconia” Appl. Phys. Lett. 71 (20), pp. 2955-2957, 17 Nov. 1997 and Iijima et al, “Research and Development of Biaxially Textured IBAD-GZO Templates for Coated Superconductors”, MRS Bulletin. August 2004 pp. 564-571, all incorporated herein as if fully set forth herein) to permit the formation of a 3-dimensionally ordered, crystalline thin film. Optionally a thicker layer of the metal oxide can be grown epitaxially to increase thickness and improve crystallinity. Ion beam assisted deposition (IBAD) is typically done by vacuum evaporating magnesium oxide (MgO) (source 32) while directing an ion beam 34 at an angle to the substrate 12. When the ion beam, is set to the correct energy and density, it gives bi-axially textured orientation to the MgO. This IBAD textured layer then provides a seed layer for the epitaxial growth of (RE)BCO material,

Next an optional, buffer layer 20 (FIG. 1) is grown on the IBAD layer to improve the lattice match to the (RE)BCO film. The epitaxial HTS layer is next grown, preferably using a reactive co-evaporation cyclic deposition and reaction (RCE-CDR), described in more detail, below. Lastly an optional cap layer 22 of metal, preferably silver is deposited on the HTS to provide electrical contact to the superconducting film and physical protection.

With reference to FIG. 5, the RCE-CDR uses high purity metal targets 36 of one or more of the following rare earths (Yttrium, Samarium, Gadolinium, Neodymium, Dysprosium, etc.), barium and copper in an oxygen background environment of 10⁻⁵ Torr. The film growth occurs when it passes through the oxygen pocket where the pressure is maintained at 10-30 mTorr. This deposition and film growth cycle is done at 5-10 Hz by rotating the sample holder. Heater 38 heats the substrate. After the film is fully grown it is cooled down in oxygen pressure of 600 Torr, Techniques for RCE-CDR are now known to those skilled in the art, see, e.g., Ruby et al, “High-Throughput Deposition System for Oxide Thin Film Growth By Reactive Coevaporation”, now published as US Published Application 2007/0125303, which is incorporated herein by reference for the teaching of RCE-CDR, as if fully set forth herein.

FIGS. 6, 7 and 8 relate to the same sample. FIG. 6 is a TEM image of a ReBCO film and metal capping layer. FIG. 7 is a higher magnification TEM image of a portion of the ReBCO film of FIG. 6. FIG. 8 is a graph of the critical current (J_(c) expressed in MA/cm²) as a function of angular orientation under a magnetic field of 1 Tesla of the sample of FIGS. 6 and 7.

With reference to FIGS. 6 and 7, the transmission electron microscope (TEM) images show a cross sectional sample of the ReBCO (Re is Samarium) high temperature superconductor. A silver capping layer is show at the top of FIG. 6. The TEM shows horizontal defects in the A-B plane. The spacing between the detects in the vertical direction are 10 to 25 nm. The lengths of the defects in the A-B plane are 20 to 100 nm.

The darker contrast regions show where excessive rare-earth oxide (ReOx) nucleates as nanoparticles. The particles are embedded in the entire film matrix very uniformly along the horizontal direction which is parallel to the ReBCO a,b-axis. These act as very strong vortex pinning centers which enhances the current density under magnetic field along a, b-axis direction. FIG. 8 shows that that critical current density peaks at field angles of +/−90 degrees, which corresponds to the magnetic field parallel to the a, b-axis orientation. The ratio of the peak J_(c) to the minimum J_(c) as a function of angle is preferably at most less than 2, more preferably at most less than 1.5, and most preferably at most less than 1.3.

The solution deposition planarization (SDP) layer is the starting step for the entire coated conductor stack. The layer is most preferably amorphous, preferably without any deleterious crystalline structure. It is preferably smooth for the Ion Beam Assisted Deposition (IBAD) layer which is supported by the SDP layer. While it depends on the substrate, the substrate variations may be on the order of 25 to 50 nm for a metal substrate. They are considerably less for a single crystal substrate. The roughness of the SDP layer is measured by Atomic Force Microscopy (AFM). The roughness of the SDP layer is preferably 4 nm Root Mean Square (RMS) roughness, or less. The SDP functions to perform one or more of the following functions; planarize the substrate, provide a chemically inert buffer layer, and to provide a diffusion barrier.

The films are rare earth and copper rich relative to the 1-2-3 stoichiometry, or stated otherwise, they are barium poor. The rare earth can range from 17% to 19%, and the copper can range from 52% to 55%. The substantially horizontal nature of the defects result from rare earth and copper richness at the upper end of these ranges.

FIGS. 9 and 10 show TEM images of ReBCO at two different magnifications, both showing very strong dislocations along the vertical direction which is parallel to the c-axis of the ReBCO. These vertical columnar defects or dislocations range in length from 1 micron to 3 microns. As can be seen in FIG. 9, relative peak in the critical current density peak at 0 degrees applied field angle corresponds to the c-axis in the angular in-field measurement.

Nanoparticles are also shown aligned along, the a,b-axis. FIG. 11 is a graph of the critical current (J_(c) expressed in MA/cm²) as a function of angular orientation under a magnetic field of 1 Tesla of the sample of FIGS. 9 and 10. The TEM shows horizontal defects in the A-B plane. The spacing between the defects in the vertical direction are 10 to 25 nm. The lengths of the defects in the A-B plane are 20 to 100 nm. The relative height of the peak in the critical current when the magnetic field is applied normal to the surface of the superconductor relative to the peak when the field is applied parallel to the surface is preferably greater than 50%, more preferably greater than 75%, and most preferably substantially equal to 100%.

The films are rare earth and copper rich relative to the 1-2-3 stoichiometry, or stated otherwise, they are barium poor. The range of Barium to Rare Earth (Ba/Re) is preferably in the range from 1.4 to 2.1, or more preferably in the range from 1.65 to 1.85. The atomic percent copper can range from 50% to 55%.

FIG. 12 is a graph of the critical current Ic as a function of angle from the c-axis in degrees for a sample with a barium to rare earth (Samarium (Sm)) ratio of 1.57. The properties of the coated conductor may be tuned by varying the ratio of barium to the rare earth, while controlling the atomic copper percent. The desired range for the barium to rare earth ratio (Ba/Re) is from 1.4 to 2.1. The atomic percent of copper can vary generally between 50.0 and 55.0% without impacting the resulting critical current profile.

FIG. 13 is a graph of the critical current Ic as a function of angle from the c-axis in degrees with a Ba/Sm ratio of 1.76. Again, this is within the desired range of Ba/Re from 1.4 to 2.1. A pronounced peak at substantially zero (0) angle from the c-axis can be seen. The relative height of the peak at zero angle compared to the peak height at +/−90 degrees is substantially 100%. As compared to FIG. 12, the Ba/Re ratio is higher, or stated otherwise, less rare earth rich. By varying the Ba/Re ratio, while generally maintaining the atomic percent of copper between 50.0% and 55.0%, the performance curve of Ic as a function of angle may be set as desired. A product is preferably made by the process of reactive coevaporation cyclic deposition and reaction (RCE-CDR).

FIG. 14 is a graph of the critical current Ic as a function of angle from the c-axis in degrees with a Ba/Sm ratio of 2.02. The Ba/Re (Samarium Sm for this sample) is 2.02. As compared to FIGS. 12 and 13, the Ba/Re ratio is higher, or slated otherwise, less rare earth rich. Again, by varying the Ba/Re ratio, while generally maintaining the atomic percent of copper between 50.0% and 55.0%, the performance curve of Ic as a function of angle may be set as desired. As with the results in FIG. 13, the relative height of the peak at zero angle compared to the peak height at +/−90 degrees is substantially 100%.

FIG. 15 is a graph of the critical current density Jc as a function of angle from the c-axis in degrees with varying ratios of relative rare earth %, ranging from −5% to +20%. The relative rare earth percentage (Re %) directly affects the in-field performance. The films for FIG. 15 are 0.7 μm on single crystal MgO. The magnetic field was 0.9 T, The temperature was 77 K. By varying the relative rare earth percent, the film performance may be tuned as desired. These films range from relatively rare earth poor (−5%) to on 1:2:3 stoichiometry (0%) to moderately rare earth rich (+5%, 7.5% and 10%) to significantly rare earth rich (+20%). By tuning the relative rare earth percentage, the profile, of the film performance as a function of angle may be changed from having a relatively high response at zero angle relative to +/−90 degrees (e.g., −5%) curve), to having relatively high=/−90 degree response with little or no zero angle response.

FIG. 16 is a graph of the critical current density Jc as a function of angle from the c-axis in degrees in a sample with the vertical dislocations shown in FIG. 17 FIG. 17 is a microphotograph showing the vertical dislocations resulting in the strong c-axis peak of FIG. 16. The Ba/Re ratio is substantially 1.73. The microphotograph shows distinct vertical dislocations, generally ranging from 500 nm to over 1,000 nm. The vertical dislocations contribute to the strong c-axis peak. The process of control of the amount of vertical dislocations and horizontal dislocations, through varying the Ba/Re ratio, while generally maintaining the atomic percent of copper in the range of 50% to 55%, permits the design and implementation of responses having substantially uniform.

FIG. 18 is a plot of the critical current (I_(c)) (left vertical axis) and critical current, density (J_(c)) (right vertical axis) as a function, of magnetic field strength applied parallel to the sample, for two different temperatures. The graph shows the critical current of (RE)BCO grown on flexible metal tape measured in magnetic field at different temperatures. As the magnetic field increases the critical current decreases. At a field of 3 T, with the magnetic field parallel to the film, the I_(c) is approximately 290 A/cm-width, and J_(c) is approximately 0.66 MA/cm². The upper data set is at 65 K and the lower data set is at 75 K.

FIG. 19 is a plot of the critical current (I_(c)) (left vertical axis) and critical current density (J_(c)) (right vertical axis) as a function of the angle from the c-axis applied to the sample. FIG. 19 shows the critical current of the same sample as in FIG. 30 measured at 75 K as a function of the angle of the applied magnetic field, it shows a very strong peak when the magnetic field is perpendicular to the film normal. The upper data set is at 75 K in a 3 T field, and the lower data set is at 75 K in a 5 T field.

FIG. 20 is a plot of the critical current (I_(c)) (left vertical axis) and critical current density (J_(c)) (tight vertical axis) as a function of magnetic field strength applied parallel to the sample. FIG. 20 is the same type of measurement as FIG. 19 but done at a lower temperature of 65 K. The critical current increases significantly when cooled from 75 K. At 65 K and 3 T the minimum critical current is 250 A. The upper data set is at 65 K in a 3 T field, and the lower data set is at 55 K in a 5 T field.

FIG. 21 is a plot of the critical current (I_(c)) (left vertical axis) and critical current density (J_(c)) (right vertical axis) as a function of magnetic field strength applied parallel to the sample, at two different temperatures. It shows the critical current of the same (RE)BCO deposited on single crystal. MgO instead of the metal tape. This was measured in magnetic field at different temperatures under the same condition as FIG. 30. The minimum critical current improves roughly 50% when (RE)BCO is grown on single crystal. The upper data set is at 65 K and the lower data set is at 75 K.

FIG. 22 is a plot of the critical current density (J_(c)) (left vertical axis) and critical current (I_(c)) (right vertical axis) as a function of magnetic field strength applied parallel to the sample. FIG. 22 shows the critical current of the sample grown on single crystal MgO measured at 65 K as a function of the angle of the applied magnetic field. Comparing FIG. 20 to FIG. 22 shows a minimum critical current improvement of 80%. The uppermost data set is at 3 T, the middle data set is at 5 T and the bottom data set is at 7 T.

FIG. 23 is a plot of the critical current density (J_(c)) as a function of the angle from the c-axis of the magnetic field applied to a three different NdBCO samples. The field is 1 T, at 75.5 K. At angle 0, the uppermost data set is for a field of 1 T, with NdBCO of thickness 0.7 μm, the middle data set is for a field of 0.9 T, for Nd_(1.11)BCO of thickness 0.7 μm, and the bottom data set is for a field of 1 T for NdBCO of thickness 1.4 μm. The off-stoichiometry for Nd rich films significantly enhanced the minimum J_(c) values, by approximately a factor of 4.

FIG. 24 is a plot of the critical current density (J_(c)) as a function of the angle from the c-axis of the magnetic field applied to a three different SmBCO samples and one NdBCO sample. FIG. 24 may be compared to FIG. 23 for the difference between the two rare earths (Nd and Sm). At angle 0, the uppermost data set is for a field of 0.9 T, with Sm_(1.1)BCO of thickness 0.7 μm, the second data set is for a field of 0.9 T, for Sm_(1.1)BCO of thickness 0.8 μm, the third, data set is for a field of 0.9 T, for Sm_(1.2)BCO of thickness 0.86 μm, and the bottom data set is for a field of 0.9 T for NdBCO of thickness 0.7 μm. The off-stoichiometry for Sm rich films significantly enhanced the minimum J_(c) values, especially those having a Sm enhancement of substantially 1.1, or 10%.

FIG. 25 is a plot of the critical current density (J_(c)) as a function of the angle from the c-axis of the magnetic field applied to a series of SmBCO samples having various thicknesses. At angle 0 the upper most data are for the 0.7 μm film, the 1.6 μm film, then the 4.4 μm film, then the 3.3 μm film, with the 2.2 μm film showing at angle 0 as the lowest datapoint. For films less than 1.6 μm, and particularly for films at substantially 2.2 μm and thicker, the angular dependence of the J_(c) is essentially flat.

FIGS. 14 A and B show X-ray diffraction patterns showing 2θ−ω and ω scans for: FIG. 26A YBCO on MgO single crystal and FIG. 26B YBCO on IBAD/epitaxial MgO on SDP Hastelloy. The Δ2θ is preferably less than 0.2, more preferably less than 0.1, and most preferably less than 0.050. The Δω is preferably less than 0.5, more preferably less than 0.36, and most preferably less than 0.15. These results establish that the films are of very high crystal quality.

FIG. 27 shows the X-ray diffraction pattern of (RE)BCO grown on metal tape substrate, (001) peaks are well defined and it is a clear indication, that the HTS is growing c-axis orientated. There are no signs of poly crystalline material nor evidence of a, b oriented growth.

FIG. 28 is a X-ray diffraction pole of (RE)BCO (103) peak which shows that in-plane texture is well defined having four strong peaks.

FIG. 29 is an Atomic Force Microscopy (AFM) image showing the surface image of a thin layer of silver deposited on (RE)BCO grown on metal substrate. The large particles are copper oxide covered by silver and the short needle-like microstructure comes from the silver grains grown on top of (RE)BCO.

FIG. 30 is a resistivity vs. temperature curve of (RE)BCO grown on MgO single crystal substrate. The single crystal was inserted next to the metal substrate as a process monitor. This particular sample had a critical temperature of 93.7 Kelvin.

FIGS. 31 A, B and C are graphs of critical current (I_(c)) under magnetic field of 0.66 T as a function of position along a tape for a 70 cm long tape (FIG. 31A), a 120 cm long tape (FIG. 31B) and a 24 cm long tape (FIG. 31C), for self-field at 77 K.

Experimental

High temperature superconductor (RE)BCO is deposited on 2 different types of substrates: flexible metal substrate and single crystal magnesium oxide. The dimension of the metal tape is 4 cm long, 1 cm wide and 0.004 inch thick. Solution deposition layer of metal oxide is deposited on the metal substrate followed by ion beam assisted deposition of magnesium oxide. Single crystal magnesium oxide substrate is cut into 1 cm length, 1 cm width and 0.02 inch thick piece and crystal orientation is (100).

The method of deposition is reactive co-evaporation. High purity metal targets of rare earths (yttrium, samarium, gadolinium, neodymium, dysprosium, etc.), barium and copper are used for evaporation. Barium and copper can be evaporated with a thermal source, whereas most of the rare earths require electron beam source because of their high melting temperature. Samarium is an exception due to its nature to sublimate. It is easily deposited with special thermal source with baffles. The evaporation rate is monitored and controlled by quartz crystal monitors (QCM). Each elemental source has its own QCM directed line-of-sight through multiple collimators. The oxygen is directly supplied through the heater and its flow is controlled by a mass flow controller. The overall background oxygen pressure is monitored by a hot cathode ion gauge. Typical background pressure during deposition is in the range of 10⁻⁵ Torr. This deposition and film growth cycle is done at 5/10 Hz by rotating the sample holder attached to the heater. The film growth occurs when the sample passes through the oxygen pocket where the pressure is maintained at 10/30 mTorr. Heater temperature ranges between 750-800° C. After the film is fully grown it is cooled down in oxygen pressure of 600 Torr.

These inventions provide cutting edge high-magnetic-field test results for second generation (2G) HTS wire. This demonstrates exceptional in-field critical current values. This world-class current-carrying capability in high magnetic field demonstrates the effectiveness of the disclosed HTS fabrication process at producing 2G HTS wire for demanding applications such as superconducting fault current limiters and high-power wind turbine generators,

The 2G HTS coated conductor sample on a template that exhibits a minimum critical current of 228 amperes (A) at a temperature of 65 Kelvin (K) in an applied magnetic field of 3 Tesla (T), corresponding to 256 A/centimeter (cm)-width. This critical current is the minimum value as a function of magnetic field angle. The maximum critical current of this sample at 65 K exceeded 404 A/cm-width for a 3-T magnetic field oriented parallel to the coated conductor surface; this latter current value was limited by the amount of current supplied by the measurement apparatus. In a 5 T field at 65 K, the coated conductor exhibited a minimum critical current of 143 A/cm-width and a maximum critical current of 322 A/cm-width.

This sample was fabricated using a straightforward HTS structure and did not need to add additional elements or so-called artificial pinning centers to the coated conductor to obtain this result.

These 2G HTS wires utilize HTS material deposition processes and volume manufacturing to produce energy-efficient, cost-effective, and high-performance 2G HTS wire for next generation power applications. 2G HTS wire is fabricated using its deposition technology known as reactive coevaporation with cyclic deposition and reaction (RCE-CDR). This specific sample of 2G HTS wire is 8.9 millimeters wide×4.4 microns thick and was grown on a 1-cm-wide×4-cm-long template. This simplified template contained a reduced number of layers compared to competing 2G HTS wire technologies. The template consisted of a non-magnetic nickel-alloy substrate followed by layers of only two materials: a solution-deposition planarization (SDP) layer and an ion-beam assisted deposition (IBAD) layer. An advantage of the RCE-CDR technology is that it allows high-performance 2G HTS wire to be grown on these simplified templates. This simplified template platform combined with the RCE-CDR process results in a superior high-yield, low-cost 2G HTS wire technology.

Applications

Coated conductors are useful in a wide variety of applications including but not limited to high power transmission cables (AC), superconducting fault current limiters, wind turbine (generator), industrial motors and generators, and magnetic resonance imaging machines,

All publications and patents cited in this specification are herein incorporated by reference as if each individual publication or patent application were specifically and individually indicated to be incorporated by reference. Although the foregoing invention has been described in some detail by way of illustration and example for purposes of clarity and understanding, it may be readily apparent to those of ordinary skill in the art in light of the teachings of this invention that certain changes and modifications may be made thereto without departing from the spirit or scope of the following claims. 

We claim:
 1. A method for forming a coated superconductor comprising the steps of: providing a substrate, forming a (Re)BaCO superconductor supported by the substrate, the superconductor adapted to carry current in a superconducting state, where Re is a rare earth, Ba is barium, C is copper and O is oxygen, where the ratio of B to Re is in the range from 1.4 to 2.1, and the atomic percent copper is between substantially 50% and 55%, containing only intrinsic pinning centers, the superconductor being formed by the process including reactive coevaporation cyclic deposition and reaction (RCE-CDR), and the superconductor characterized in having a minimum critical current density (J_(c)), the J_(c) having a first peak value when the field is applied perpendicular (0 degrees) to the substrate and a second peak value when the field is applied parallel (+/−90 degrees) to the substrate, and that the ratio of the peak values being within the ranges of at least one of (i) the first peak value to the second peak value being in the range from 3:1 to 1:1 and (ii) the ratio of the first peak value to the second peak value being in the range from greater than substantially 50% to substantially equal to 100%.
 2. The method for forming a coated conductor of claim 1 wherein the ratio of the first peak value to the second peak value is greater than substantially 75%.
 3. The method for forming a coated conductor of claim 1 wherein the ratio of the first peak value to the second peak value is substantially 100%.
 4. The method for forming a coated conductor of claim 1 further characterized in that the superconductor includes horizontal defects and columnar defects in a size and an amount sufficient to result in a critical current (J_(c)) of at least 0.2 MA/cm² in a magnetic field of about 1 Tesla at 77 K when the field is applied normal to the surface of the superconductor and when the field is applied parallel to the surface of the superconductor.
 5. The method for forming a coated conductor of claim 1 wherein the substrate is flexible.
 6. The method for forming a coated conductor of claim 5 wherein the flexible substrate is a flexible metal tape.
 7. The method for forming a coated conductor of claim 6 wherein the flexible metal tape is Hastelloy.
 8. The method for forming a coated conductor of claim 6 wherein the flexible metal tape is stainless steel.
 9. The method for forming a coated conductor of claim 1 further including providing a planarization layer disposed between the substrate and the (RE)BCO.
 10. The method for forming a coated conductor of claim 9 wherein the planarization layer is a solution deposition planarization layer.
 11. The method for forming a coated conductor of claim 1 further including the step of providing an intermediate layer between the substrate and the (RE)BCO.
 12. The method for forming a coated conductor of claim 11 wherein the intermediate layer is an ion beam assisted deposition (IBAD) epitaxial layer. 